Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries.

An anion-rich electric double layer (EDL) region is favorable for fabricating an inorganic-rich solid-electrolyte interphase (SEI) towards stable lithium metal anode in ester electrolyte. Herein, cetyltrimethylammonium bromide (CTAB), a cationic surfactant, is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating. In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO3-/FSI- anions in the EDL region due to the positively charged CTA+. In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI, which helps improve the kinetics of Li+ transfer, lower the charge transfer activation energy, and homogenize Li deposition. As a result, the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm-2 with a capacity of 1 mAh cm-2. Moreover, Li||LiFePO4 and Li||LiCoO2 with a high cathode mass loading of > 10 mg cm-2 can be stably cycled over 180 cycles.

Controllable hierarchical self-assembly: systematic study forming metallosupramolecular frameworks on the basis of helical beta-oligoamides.

Self-assembly is a key guiding principle for the design of complex nanostructures. Substituted beta oligoamides offer versatile building blocks that can have inherent folding characteristics, offering geometrically defined functionalities that can specifically bind and assemble with predefined morphological characteristics. In this work hierarchical self-assembly is implemented based on metal coordinating helical beta-oligoamides crosslinked with transition metals selected for their favourable coordination geometries, Fe2+, Cu2+, Ni2+, Co2+, Zn2+, and two metalates, MoO42-, and WO42-. The oligoamide Ac-ß3Aß3Vß3S-αHαHαH-ß3Aß3Vß3A (3H) was designed to allow crosslinking via three distinct faces of the helical unit, with a possibility of forming three dimensional framework structures. Atomic force microscopy (AFM) confirmed the formation of specific morphologies that differ characteristically with each metal. X-Ray photoelectron spectroscopy (XPS) results reveal that the metal centres can be reduced in the final structures, confirming strong chemical interaction. Time of flight secondary ion mass spectrometry (ToF-SIMS) confirmed the spatial distribution of metals within the self-assembled networks, also revealing molecular fragments that confirm coordination to histidine and carboxyl moieties. The metalates MoO42- and WO42- were also able to induce the formation of specific superstructure morphologies. It was observed that assembly with either of nickel, copper, and molybdate form thin films, while cobalt, zinc, and tungstate produced specific three dimensional networks of oligoamides. Iron was found to form both a thin film and a complex hierarchical assembly with the 3H simultaneously. The design of the 3H substituted beta oligoamide to readily form metallosupramolecular frameworks was demonstrated with a range of metals and metalates with a degree of control over layer thicknesses as a function of the metal/metalate. The results validate and broaden the metallosupramolecular framework concept and establish a platform technology for the design of functional thin layer materials.

Experimental and Numerical Study of Al2219 Powders Deposition on Al2219-T6 Substrate by Cold Spray: Effects of Spray Angle, Traverse Speed, and Standoff Distance.

Cold spray (CS) is an emerging technology for repairing and 3D additive manufacturing of a variety of metallic components using deformable metal powders. In CS deposition, gas type, gas pressure, gas temperature, and powder feed rate are the four key process parameters that have been intensively studied. Spray angle, spray gun traverse speed, and standoff distance (SoD) are the other three process parameters that have been less investigated but are also important, especially when depositing on uneven substrates or building up 3D freeform structures. Herein, the effects of spray angle, traverse speed, and SoD during CS deposition have been investigated holistically on a single material system (i.e., Al2219 powders on Al2219-T6 substrate). The coatings' mass gain, thickness, porosity, and residual stress have been characterized, and the results show that spray angle and traverse speed exercise much more effects than SoD in determining coatings' buildup. Finite element method (FEM) modeling and computational fluid dynamic (CFD) simulation have been carried out to understand the effects of these three parameters for implementing CS as repairing and additive manufacturing using aluminum-based alloy powders.

Greatly Enhanced Resonant Exciton-Trion Conversion in Electrically Modulated Atomically Thin WS2 at Room Temperature.

Excitonic resonance in atomically thin semiconductors offers a favorite platform to study 2D nanophotonics in both classical and quantum regimes and promises potentials for highly tunable and ultra-compact optical devices. The understanding of charge density dependent exciton-trion conversion is the key for revealing the underlaying physics of optical tunability. Nevertheless, the insufficient and inefficient light-matter interactions hinder the observation of trionic phenomenon and the development of excitonic devices for dynamic power-efficient electro-optical applications. Here, by engaging an optical cavity with atomically thin transition metal dichalcogenides (TMDCs), greatly enhanced exciton-trion conversion is demonstrated at room temperature (RT) and achieve electrical modulation of reflectivity of ≈40% at exciton and 7% at trion state, which correspondingly enables a broadband large phase tuning in monolayer tungsten disulfide. Besides the absorptive conversion, ≈100% photoluminescence conversion from excitons to trions is observed at RT, illustrating a clear physical mechanism of an efficient exciton-trion conversion for extraordinary optical performance. The results indicate that both excitons and trions can play significant roles in electrical modulation of the optical parameters of TMDCs at RT. The work shows the real possibility for realizing electrical tunable and multi-functional ultra-thin optical devices using 2D materials.

2D Material Infrared Photonics and Plasmonics.

Two-dimensional (2D) materials including graphene, transition metal dichalcogenides, black phosphorus, MXenes, and semimetals have attracted extensive and widespread interest over the past years for their many intriguing properties and phenomena, underlying physics, and great potential for applications. The vast library of 2D materials and their heterostructures provides a diverse range of electrical, photonic, mechanical, and chemical properties with boundless opportunities for photonics and plasmonic devices. The infrared (IR) regime, with wavelengths across 0.78 µm to 1000 µm, has particular technological significance in industrial, military, commercial, and medical settings while facing challenges especially in the limit of materials. Here, we present a comprehensive review of the varied approaches taken to leverage the properties of the 2D materials for IR applications in photodetection and sensing, light emission and modulation, surface plasmon and phonon polaritons, non-linear optics, and Smith-Purcell radiation, among others. The strategies examined include the growth and processing of 2D materials, the use of various 2D materials like semiconductors, semimetals, Weyl-semimetals and 2D heterostructures or mixed-dimensional hybrid structures, and the engineering of light-matter interactions through nanophotonics, metasurfaces, and 2D polaritons. Finally, we give an outlook on the challenges in realizing high-performance and ambient-stable devices and the prospects for future research and large-scale commercial applications.

Interlayer Excitons in Transition Metal Dichalcogenide Semiconductors for 2D Optoelectronics.

Optoelectronic materials that allow on-chip integrated light signal emitting, routing, modulation, and detection are crucial for the development of high-speed and high-throughput optical communication and computing technologies. Interlayer excitons in 2D van der Waals heterostructures, where electrons and holes are bounded by Coulomb interaction but spatially localized in different 2D layers, have recently attracted intense attention for their enticing properties and huge potential in device applications. Here, a general view of these 2D-confined hydrogen-like bosonic particles and the state-of-the-art developments with respect to the frontier concepts and prototypes is presented. Staggered type-II band alignment enables expansion of the interlayer direct bandgap from the intrinsic visible in monolayers up to the near- or even mid-infrared spectrum. Owing to large exciton binding energy, together with ultralong lifetime, room-temperature exciton devices and observation of quantum behaviors are demonstrated. With the rapid advances, it can be anticipated that future studies of interlayer excitons will not only allow the construction of all-exciton information processing circuits but will also continue to enrich the panoply of ideas on quantum phenomena.

Optimisation of Lapping Process Parameters for Single-Crystal 4H-SiC Using Orthogonal Experiments and Grey Relational Analysis.

Lapping is one of the standard essential methods to realise the global planarization of SiC and other semiconductor substrates. It is necessary to deeply study the mechanism to obtain SiC lapping process parameters with a strong comprehensive lapping performance (i.e., high material removal rate (MRRm), small surface roughness (Ra), and low total thickness variation (TTV)). The effects of the lapping process parameters and their interactions on lapping performance for SiC were investigated using orthogonal experiments; the effects on the MRRm, Ra, TTV, and optimal parameters under the conditions of a single evaluation index were investigated using intuitive analysis (range analysis, variance analysis, and effect curve analysis). The entropy value method and grey relational analysis were used to transform the multi-evaluation-index optimisation into a single-index optimisation about the grey relational grade (GRG) and to comprehensively evaluate the lapping performance of each process parameter. The results showed that the lapping plate types, abrasive size, and their interaction effect had the most significant effects on MRRm and Ra, with a contribution of over 85%. The interaction between the lapping plate types and abrasive size was also found to have the most significant effect on TTV, with a contribution of up to 51.07%. As the lapping plate's hardness and abrasive size increased, the MRRm and Ra also gradually increased. As the lapping normal-pressure increased, MRRm increased, Ra gradually decreased, and TTV first decreased and then increased. MRRm, Ra, and TTV first increased and then decreased with increasing abrasive concentration. Compared to the optimisation results obtained by intuitive analysis, the process parameter optimised by the grey relational analysis resulted in a smooth surface with an MRRm of 90.2 µm/h, an Ra of 0.769 nm, and a TTV of 3 µm, with a significant improvement in the comprehensive lapping performance. This study reveals that a combination of orthogonal experiments and grey relational analysis can provide new ideas for optimising the process parameters of SiC.

Analysis of perovskite oxide etching using argon inductively coupled plasmas for photonics applications.

We analyzed the dry etching of perovskite oxides using argon-based inductively coupled plasmas (ICP) for photonics applications. Various chamber conditions and their effects on etching rates have been demonstrated based on Z-cut lithium niobate (LN). The measured results are predictable and repeatable and can be applied to other perovskite oxides, such as X-cut LN and barium titanium oxide (BTO). The surface roughness is better for both etched LN and BTO compared with their as-deposited counterparts as confirmed by atomic force microscopy (AFM). Both the energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) methods have been used for surface chemical component comparisons, qualitative and quantitative, and no obvious surface state changes are observed according to the measured results. An optical waveguide fabricated with the optimized argon-based ICP etching was measured to have -3.7 dB/cm loss near 1550 nm wavelength for Z-cut LN, which validates this kind of method for perovskite oxides etching in photonics applications.

Realization of Self-Compliance Resistive Switching Memory via Tailoring Interfacial Oxygen.

Self-compliance set switching (SCSS) offers the promise of a selector-less resistive random access memory (RRAM) implementation on flexible substrates, with great application in integrated flexible electronics. SCSS has been realized in RRAM devices with a series oxide layer incorporated into the memory stack. The series oxide acts as an in-built resistor, limiting the increase of the current during set transition. In this study, we show that SCSS can also be achieved in a bipolar RRAM cell without a series oxide layer, i.e., consisting of only a single switching oxide layer. This study reveals that oxygen pileup at the anode interface during the set evolution plays a crucial role in SCSS. The accumulation of oxygen gives rise to the increase of the switching oxide resistance, partially compensating the decrease of the filament resistance, and modulates the conduction barrier at the anode/oxide interface, which self-arrests the increase of the set switching current. Our results show interface engineering as a possible route for enabling SCSS in an RRAM device without the need for a complicated stack structure and careful thickness optimization.

A Nanomechanical Analysis of Deformation Characteristics of 6H-SiC Using an Indenter and Abrasives in Different Fixed Methods.

The super-precise theory for machining single crystal SiC substrates with abrasives needs to be improved for its chemical stability, extremely hard and brittle. A Berkovich indenter was used to carry out a systematic static stiffness indentation experiments on single crystal 6H-SiC substrates, and then these substrates were machined by utilizing fixed, free, and semi-fixed abrasives, and the nanomechanical characteristics and material removal mechanisms using abrasives in different fixed methods were analyzed theoretically. The results indicated that the hardness of C faces and Si faces of single crystal 6H-SiC under 500 mN load were 38.596 Gpa and 36.246 Gpa respectively, and their elastic moduli were 563.019 Gpa and 524.839 Gpa, respectively. Moreover, the theoretical critical loads for the plastic transition and brittle fracture of C face of single crystal 6H-SiC were 1.941 mN and 366.8 mN, while those of Si face were 1.77 mN and 488.67 mN, respectively. The 6H-SiC materials were removed by pure brittle rolling under three-body friction with free abrasives, and the process parameters determined the material removal modes of 6H-SiC substrates by grinding with fixed abrasives, nevertheless, the materials were removed under full elastic-plastic deformation in cluster magnetorheological finishing with semi-fixed abrasives.

A bilayer swellable drug-eluting ureteric stent: Localized drug delivery to treat urothelial diseases.

A bilayer swellable drug-eluting ureteric stent (BSDEUS) is engineered and implemented, as a sustained drug delivery platform technology that enhances localized drug delivery to the highly impermeable urothelium, for the treatment of urothelial diseases such as strictures and carcinomas. On deployment, the device swells to co-apt with the ureteric wall and ensure drug availability to these tissues. BSDEUS consists of a stent spray-coated with a polymeric drug containing polylactic acid-co-caprolactone (PLC) layer which is overlaid by a swellable polyethylene glycol diacrylate (PEGDA) based hydrogel. In-vitro quantification of released drug demonstrated a tunable time-profile, indicating sustained delivery over 1-month. The PEGDA hydrogel overlayer enhanced drug release and transport into explanted porcine ureteric tissues ex-vivo, under a simulated dynamic fluid flow. A preliminary pilot in-vivo feasibility study, in a porcine model, demonstrated that the swollen hydrogel co-apts with the urothelium and thus enables localized drug delivery to the target tissue section. Kidney functions remained unaffected and device did not result in either hydronephrosis or systemic toxicity. This successful engineering of a bilayer coated stent prototype, demonstrates its feasibility, thus offering a unique solution for drug-based urological therapy.

Modification of Vapor Phase Concentrations in MoS2 Growth Using a NiO Foam Barrier.

Single-layer molybdenum disulfide (MoS2) has attracted significant attention due to its electronic and physical properties, with much effort invested toward obtaining large-area high-quality monolayer MoS2 films. In this work, we demonstrate a reactive-barrier-based approach to achieve growth of highly homogeneous single-layer MoS2 on sapphire by the use of a nickel oxide foam barrier during chemical vapor deposition. Due to the reactivity of the NiO barrier with MoO3, the concentration of precursors reaching the substrate and thus nucleation density is effectively reduced, allowing grain sizes of up to 170 µm and continuous monolayers on the centimeter length scale being obtained. The quality of the monolayer is further revealed by angle-resolved photoemission spectroscopy measurement by observation of a very well resolved electronic band structure and spin-orbit splitting of the bands at room temperature with only two major domain orientations, indicating the successful growth of a highly crystalline and well-oriented MoS2 monolayer.

XPS Study on the Stability and Transformation of Hydrate and Carbonate Phases within MgO Systems.

MgO cements have great potential for carbon sequestration as they have the ability to carbonate and gain strength over time. The hydration of reactive MgO occurs at a similar rate as ordinary Portland cement (PC) and forms brucite (Mg(OH)2, magnesium hydroxide), which reacts with CO2 to form a range of hydrated magnesium carbonates (HMCs). However, the formation of HMCs within the MgO-CO2-H2O system depends on many factors, such as the temperature and CO2 concentration, among others, which play an important role in determining the rate and degree of carbonation, the type and stability of the produced HMCs and the associated strength development. It is critical to understand the stability and transformation pathway of HMCs, which are assessed here through the use of X-ray photoelectron spectroscopy (XPS). The effects of the CO2 concentration (in air or 10% CO2), exposure to high temperatures (up to 300 °C) and curing period (one or seven days) are reported. Observed changes in the binding energy (BE) indicate the formation of different components and the transformation of the hydrated carbonates from one form to another, which will influence the final performance of the carbonated blends.

Defect assisted coupling of a MoS2/TiO2 interface and tuning of its electronic structure.

Although MoS2 based heterostructures have drawn increased attention, the van der Waals forces within MoS2 layers make it difficult for the layers to form strong chemical coupled interfaces with other materials. In this paper, we demonstrate the successful strong chemical attachment of MoS2 on TiO2 nanobelts after appropriate surface modifications. The etch-created dangling bonds on TiO2 surfaces facilitate the formation of a steady chemically bonded MoS2/TiO2 interface. With the aid of high resolution transmission electron microscope measurements, the in-plane structure registry of MoS2/TiO2 is unveiled at the atomic scale, which shows that MoS2[1-10] grows along the direction of TiO2[001] and MoS2[110] parallel to TiO2[100] with every six units of MoS2 superimposed on five units of TiO2. Electronically, type II band alignments are realized for all surface treatments. Moreover, the band offsets are delicately correlated to the surface states, which plays a significant role in their photocatalytic performance.

ING4 Inhibits Proliferation and Induces Apoptosis in Human Melanoma A375 Cells via the Fas/Caspase-8 Apoptosis Pathway.

BACKGROUND: Inhibitor of growth 4 (ING4) plays a role in regulating the cell cycle, apoptosis, cell invasion and migration, but the mechanisms involved remain to be elucidated. OBJECTIVE: To explore how ING4 affects human malignant melanoma A375 cells. METHODS: Recombinant lentiviral vectors (A375/pLenO-GTP-ING4) were constructed and transfected into A375 cells (experimental group). The impact of ING4 on the proliferation and apoptosis of A375 cells was investigated in in vitro and in vivo experiments in mice using the MTT assay and flow cytometry. RESULTS: In the experimental group, optical density was lower and apoptotic cells were more frequent from days 2-5 (p = 0.000 and p < 0.01); there were smaller xenografts and more apoptotic cells in mice (all p < 0.05); moreover, increased levels of Fas, cleaved caspase-8 and caspase-3, and decreased levels of FasL and procyclic acidic repetitive protein were observed in vitro and in vivo. CONCLUSION: ING4 might suppress proliferation and enhance apoptosis in human malignant melanoma cells by activating Fas-induced apoptosis in a caspase-8-dependent pathway.

Thickness-Induced Metal-Insulator Transition in Sb-doped SnO2 Ultrathin Films: The Role of Quantum Confinement.

A thickness induced metal-insulator transition (MIT) was firstly observed in Sb-doped SnO2 (SnO2:Sb) epitaxial ultrathin films deposited on sapphire substrates by pulsed laser deposition. Both electrical and spectroscopic studies provide clear evidence of a critical thickness for the metallic conductivity in SnO2:Sb thin films and the oxidation state transition of the impurity element Sb. With the shrinkage of film thickness, the broadening of the energy band gap as well as the enhancement of the impurity activation energy was studied and attributed to the quantum confinement effect. Based on the scenario of impurity level pinning and band gap broadening in quantum confined nanostructures, we proposed a generalized energy diagram to understand the thickness induced MIT in the SnO2:Sb system.

Growth of wafer-scale MoS2 monolayer by magnetron sputtering.

The two-dimensional layer of molybdenum disulfide (MoS2) exhibits promising prospects in the applications of optoelectronics and valleytronics. Herein, we report a successful new process for synthesizing wafer-scale MoS2 atomic layers on diverse substrates via magnetron sputtering. Spectroscopic and microscopic results reveal that these synthesized MoS2 layers are highly homogeneous and crystallized; moreover, uniform monolayers at wafer scale can be achieved. Raman and photoluminescence spectroscopy indicate comparable optical qualities of these as-grown MoS2 with other methods. The transistors composed of the MoS2 film exhibit p-type performance with an on/off current ratio of ∼10(3) and hole mobility of up to ∼12.2 cm(2) V(-1) s(-1). The strategy reported herein paves new ways towards the large scale growth of various two-dimensional semiconductors with the feasibility of controllable doping to realize desired p- or n-type devices.

Anisotropic conductive films based on highly aligned polyimide fibers containing hybrid materials of graphene nanoribbons and carbon nanotubes.

Anisotropic electrically conductive films (PI-GNR/CNT) consisting of highly aligned polyimide (PI) composite fibers with graphene nanoribbon (GNR) and carbon nanotube (CNT) (GNR/CNT) hybrids as nanofillers have been prepared by electrospinning. The GNR/CNT hybrids used here were prepared by one-step partial unzipping of multi-walled CNTs, in which, with the residual CNTs bonded on the randomly arranged GNR sheets, not only the aggregation of GNR sheets was greatly prevented but also an electrically conductive pathway with good conductivity was effectively formed with the CNTs acting as linking bridges between different GNRs. Due to the three-dimensional (3D) conductive network structure of the GNR/CNT hybrid and fine dispersion and alignment inside the PI fibers, as well as the good interfacial interaction between the GNR/CNT hybrid and the PI matrix, PI-GNR/CNT composite films exhibit a unique property of anisotropic electrical conductivity of 8.3 × 10(-2) S cm(-1) in the parallel direction along the fibers and 7.2 × 10(-8) S cm(-1) in the perpendicular direction, which may open the way for wide potential applications of anisotropic conductive nanomaterials in practical production and scientific research fields.

Synthesis of few-layered MoS2 nanosheet-coated electrospun SnO2 nanotube heterostructures for enhanced hydrogen evolution reaction.

In this work, we report the fabrication of low crystalline, few-layered MoS2 nanosheet-coated electrospun SnO2 nanotube (MoS2/SnO2) heterostructures with three-dimensional configurations by electrospinning combined with a one-step solvothermal approach. The morphologies and compositions of the as-prepared hybrid nanotubes were characterized by field-emission scanning electron microscopy, transmission electron microscopy, ICP-AES, BET method, X-ray diffraction and X-ray photoelectron spectroscopy. Results show that SnO2 nanotubes are uniformly covered by sheet-like MoS2 subunits on both outer and inner surfaces. The electrocatalytic activity of MoS2/SnO2 heterostructures towards a hydrogen evolution reaction was examined using linear sweep voltammetry and AC impedance measurements. It is shown that the MoS2/SnO2 modified electrode exhibits excellent catalytic activity for hydrogen evolution with low overpotential, a small Tafel slope and high current density.

One-step synthesis of graphene nanoribbon-MnO2 hybrids and their all-solid-state asymmetric supercapacitors.

Three-dimensional (3D) hierarchical hybrid nanomaterials (GNR-MnO2) of graphene nanoribbons (GNR) and MnO2 nanoparticles have been prepared via a one-step method. GNR, with unique features such as high aspect ratio and plane integrity, has been obtained by longitudinal unzipping of multi-walled carbon nanotubes (CNTs). By tuning the amount of oxidant used, different mass loadings of MnO2 nanoparticles have been uniformly deposited on the surface of GNRs. Asymmetric supercapacitors have been fabricated with the GNR-MnO2 hybrid as the positive electrode and GNR sheets as the negative electrode. Due to the desirable porous structure, excellent electrical conductivity, as well as high rate capability and specific capacitances of both the GNR and GNR-MnO2 hybrid, the optimized GNR//GNR-MnO2 asymmetric supercapacitor can be cycled reversibly in an enlarged potential window of 0-2.0 V. In addition, the fabricated GNR//GNR-MnO2 asymmetric supercapacitor exhibits a significantly enhanced maximum energy density of 29.4 W h kg(-1) (at a power density of 12.1 kW kg(-1)), compared with that of the symmetric cells based on GNR-MnO2 hybrids or GNR sheets. This greatly enhanced energy storage ability and high rate capability can be attributed to the homogeneous dispersion and excellent pseudocapacitive performance of MnO2 nanoparticles and the high electrical conductivity of the GNRs.